Method of improving the dyeing properties of artificial textile materials



Patented July 28, 1942 UNITED STATES PATENT OFFICE METHOD OF IMPROVING THE DYEING PROPERTIES OF ARTIFICIAL TEXTILE MATERIALS Paul Schlack, Berlin-Treptow, Germany, assignor, by mesne assignments, to

berg, New York, N. Y.

No Drawing. Application February 17, 1939, Se-

rial No. 256,857. In Germany February 11,

Claims.

I have proposed (U. s. Patent No. 2,131,145

to modify more or less profoundly, especially in respect of afilnity and fastness to dyestufis, the chemical character of textile materials which consist of or contain protein substances or derivatives or conversion products thereof by action of an alkyleneoxide or a derivative or analogue thereof which may contain in addition to the reactive heterocyclic ring a basic or an acid group, for instance ethyleneoxide, 1:2-prbpyleneoxide, epichlorhydrin, piperido-propenoxide, 1 2-propylenesulfide, 1-chl0ro-2 3-propylenesulfide, N-butyl-ethyleneimine, N-diethyl ethylene iminium chloride, sodium-2.3-epoxypropane-1- sulfonate.

During this reaction substitution occurs at the basic as well as at the acid groups, coupled with a. shifting of the iso-electric point or region. In most cases the absorption capacity for acid dyestufl's is increased and that for :basic dyestuffs diminished, however, the conditions may be changed completely if the substituting residues contain acid groups, especially sulfa-groups.

I have also shown (U. S. Patent No. 2,131,146) that textile materials of protein substances and other basic materials of high molecular weight, which contain residues capable of being alkylated. may be converted in a similar manner and with similar results .with mixtures of alkylene oxide and the reactive alkyl ester of an inorganic or an organic-inorganic acid. Finally, I have recommended (U. S. Patent No. 2,131,121) that textiles, which contain basic residues attached to natural or artificial polymeric bodies, and which are dyed with acid dyes should be after-treated with alkyleneoxides orderivatives or analogues thereof for the purpose of improving the fastness of the dyeing.

Especially strong effects of this type, which may be connected with a decrease of the swelling capacity in an alkaline medium, are ob- 'tained by means of polyfunctional compounds of the type of epichlorhydrin.

In the U. S. Patent No. 2,097,120 it has further been proposed to introduce nitrogen into viscose rayon by treating the same with ethylene- Walther H. Duisprovide a method of improving the dyeing .properties of cellulose organic ester silk, and particularly of cellulose acetate rayon, which contains incorporated and fixed therein a certain amount of basic-reacting groups capable of being alkylated.

A further object of the invention consists inthe provision of improved fibers of the kind re ferred to, which may be more easily and fastly dyed than cellulose ester threads, which have merely been subjected to a process, by which basic groups are introduced thereinto.

Still further objects of the-inventionwill appear as the following description proceeds.

The method of the invention consists in treating artificial textile materials produced from organophil organic esters of cellulose, which textile materials contain incorporated and fixed therein basic groups, with an alkyl'eneimine, -oxide, or -sulf 1de before dyeing the same with an acid dye.

(The term organophil denotes compounds which are soluble or at least capable of swelling strongly inorganic solvents.)

The organic ester silk may contain a basic radical linked to the molecule chemically for instance the reaction product of cellulose derivatives with halogen alkylamines, halogen hydroxyalkylamines, ethylene imines and ethylene imine derivatives, or substituted aminopropenoxides.

It may vfurthermore contain an additional component for instance a resinous basic component.

Examples of such additional components are basic substituted polymerizates, for example of the polyvinyl alcohol orpolyacrylic acid series, for instance the reaction product of polyvinyl alcoholate with halogen alkylamines, the condensation products of polyacrylic acid methyl ester and aliphatic polyamines, such as p-diethylaminoethylamine; also basic aldehyde resins, for

example basic toluene arylsulfamide resins, basic phenol aldehyde resins, or basic alkyde resins.-

A number of such resins are for instance described in the applications Ser. No. 47,638 filed .imine. If necessary the treatment may be re- 'October 31, 1935, and Ser. No. 64,776 filed ruary 19, 1936, Patent No. 2,183,754.

In the case of basic phenol resins as additions the treatment with the alkylene oxide has the particular advantage that it often improves essentially the stability of the product to light.

By the action of the alkylene oxides, -imin es and -sulfides the reactivity of the textile materials particularly the aflinity for dyestufis, is con siderably modified so that various effects become possible. Depending upon the selection of the Feb- 2" mum, the met. an or the amnitytobasic dyestuffs or textile assistants may be influenced in the sired sense. Quite apart from the greater range in the choice of dyestuffs and dyeing proccases which is obtained by the invention, in many cases a considerable improvement in the fastformation of extremely fine pores in the hydrophobic substratum, thus facilitating the access of dyestuffs of considerable molecular dimensions, such as for instance chrome dyes to the basic groups or to the additional resinous components which contain such basic groups. Iihavi: found e? g. that a cellulose acetate, which contains an addition of a basic resin, and which may be dyed quite well with an ordinary simple acid wool dye, does not take up dyes of a more complicated structure, such as chrome dyes. Since these latter, however, yield-the'fastest dyeings, their employment represents a great advantage. -The same cellulose acetate, if treated according to the process of the present invention before dyeing, takes up dyes of high molecular dimensions and of completed structure easily and fixes them lastly.

For the purpose of the invention there may be used a large number of substances belonging in a narrow and in a wide sense to the class of alkylene oxides and their derivatives and having .theproperty of alkylating thecompound containing the reactive group while splitting the heterocyclic ring.. For example the following may be named: Ethylene oxide, propylene oxide, butylene oxid'e. cyclohexene oxide, phenoxypropenoxide, butadiene dioxide, slycide, epichlorhydrin, epibromhydrin, epi-iodohydrin, '1-2 propylene sulfide, 3-chlor-l.2-propylenesulfide, ethylene imine, N-butylethylene imine, N-diethylethylene iminium chloride, N-pentamethyl ene ethylene iminium chloride, the Monsternary spirocyclic compound from di'-- -chlor-phydroxypropylpiperazine. The reactive substances,-so far as they are sumciently volatile,

may with advantage be used in the form of their vapors, generally at diminished or raised pressure. Less volatile substances are used in aqueous treating liquors, padding solutions or be adapted totbefastn tiles. f coursethe working conditions have to ess of the substratum to chemical agents. For the gaseous treatment a suitable adJustmentof the relative air moisture h suiiicient. Therefore, it is necessary to find the mostv suitable working conditions for each case bysimple experiments.- With reactive com-, pounds, for instance epichlorhydrin, ethylene imine and the like a medium temperature between 40' and 80 and atime of reaction of 2 to about 16 hours will be necessary. Further details will be disclosed by the following examples. (1) Acetate artificial silk which contains percent of the basic resin obtainable from polyacrylic acid ethyl ester and an 'equimolecular proportion of p-diethylamino-ethylamine at 120' I0 130' C. (French Patent N0.'798,460) after rinsi'ng'with dilute acetic acid and drying. is heated at .92 per cent relative moisture at 80 C. with 20 per cent of vapor of epichlorhydrin for 15 hours.

' The aiiinity to many acid-,dyestufls especially to such which previously were only badly absorbed as for instance to alizarincyaningreen, is considerably increased and also the fastness wishing ofthe dyeingsisimproved.

(2) Acetate artificial silk which contains 7.5 per cent of a basicresin made by heating dimethylaminoethanol with a novolak from-l0 mol- 1 phenol and 7 mol formaldehyde in alcohol-is treated for 12 hours at 80 C. with 10 per cent of epichlorhydrin and 10 per cent of ethylene oxide at 92 per cent relative moisture. Dyeings 'on the silk with acid dyestuifs, for instance Alizarine Direct Blue A (Schultz Farbstoiftabellen 7th edition, vol. 11. page 7) have'a better tastness than they have on material which has not been pretreated in accordance with the example: The

fiber also shows a smaller tendency to yellowing.

(3) -Diethylaminoethyl cellulose made by the reaction of alkali cellulose and p-chlorodiethylamine is acetylated. Threads made from this acetyl-aminoethyl cellulose are pre-treated with very dilute hydrochloric acid and then washed with water and treated with 20 per cent of epichlorhydrin for 15 hours at 80 C. The dyeing.

. properties of the material are improved, for inprintingpastes or dissolved in organic solvents as for instance alcohol, acetone, carbontetrachloride, butanol, toluene, gasoline. The reaction maybe accelerated by catalysts, for exampleorbybases,insomecasesalsobyacidsoracid stance dyestuffs of the type of Alizarincyaningreen G Extra (Schultz. Farbstofltabellen, 7th edition, voL'I, me 532) areabsorbed in greater quantities and the dyeings obtained are faster.

Theaflinityisenhancedifinstead ofhydrochloric'acid, sulfocyanic acid is used or if an intermediate treatment with a salt of the sulfocyanic acid takes place. Instead of epichlorhydrin, 3-chloro-L2-propylene sulfide may be used.

(4) An acetate artificial silk containing 8 per cent of the product obtained by reacting chlorinated hard parafiin with superfluous ethylenedireacting salts such as aluminium chloride or sine chloride.- If desired the catalyst may be applied only locally or in the form of a pattern, whereby pattern effects may be produced. Also. the pres-' ence of condensing agents, especially of carbonyl compounds and derivatives thereof may be of advantage;

The working conditions to be observed from caseto caseas concentration of the reacting substances, time of reaction are dependent on the reactivity of the agents employed, on the capacity and degree of swelling,

, on the pH-value and on other influences, par- 'ticularlyalsoonthedegreeotdrynessotthetexacid dyestuifs.

amine is stored in a closed vessel (volume 40 cc. per. 1 gramof textile/fiber) in vapor of l0 per cent ethyleneimine for 8 hours at C. at 45 per cent relative air moisture. Subsequently it is acidified with acetic acid (3 grams per liter) at for $5 hour. -The artificial silk treated in such a manner is dyed intensively with Alisarincyaningreen G Extra (Schultz Fa'rbstofitabellen, 7th edition, vol. I. me 532) and similar The dyeing is of good quali y as regards the fastness. The fiber not after-treated with imine absorbs Alisarincyaningreen G essen- (5) An acetate artificial fiber which contained 12 per cent or the mixed polymerisate from 1 mol maleic acid anhydride and 1 mol vinylmethyletber and which immediately after the spinning process is aminated by an after-treatment with a 3 per cent solution of 3-dimethylamino-l-aminopropane in trichlorethylene is stored in a closed chamber (volume 50 cc. per 1 gram of fiber) in vapor of 12 per cent epichlorhydrin for 14 hours at 75 C. and '75 per cent relative air moisture. The afiinity to acid dyestuffs for instance Alizarincyaningreen G Extra, Azoacidblack 3 BL Extra (Ullmann, Enzyklopaedie der technischen Chemie, second edition, vol. II, page 4'!) is enhanced.

I claim:

1. A method of improving the aflinity to acid dyestufis of artificial textile materials consistin chiefly of organic cellulose esters soluble in organic solvents and containing basic reacting groups, which method comprises reacting said textile materials before dyeing with a compound selected from the group consisting of alkyleneoxides, alkyleneimines a'nd alkylenesulfldes.

2. A method of improving the aflinity to acid dyestufis'of artificial textile materials consisting chiefly of organic cellulose esters containing basic nitrogen, said cellulose ester being soluble in organic solvents, which method comprises reacting said textile materials before dyeing with a compound selected from the group consisting of alryleneoxides, alkylenelmines and alkylenesulfi es.

3. A method of improving the aflinlty to acid dyestufis of artificial textile materials consisting chiefly of organic cellulose esters soluble in organic solvents and having incorporated and fixed therein as an additional component a basic artificial resin which method comprises reacting the textile materials before dyeing with a compound selected from the group consisting of alkyleneoxides, alkyleneimines and alkylenesulfldes.

4. A method of improving the aflinlty to acid dyestufls ofartificial textile materials consisting chiefly of organic cellulose acetate having incorporated and fixed therein a basic artificial resin which method comprises reacting said textile materials beyore dyeing with a compound selected from the group consisting of alkyleneoxides, alkyleneimines and alkylenesulfldes.

5. Textile materials consisting chiefly of organic esters of cellulose and containing hydroxy alkylated basic nitrogen atoms, said materials being prepared by reacting artificial textile materials consisting chiefly of organic cellulose esters containing basic nitrogen with alkylene oxides.

PAUL SCHLACK. 

